Full metadata record
DC Field | Value | Language |
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dc.contributor.author | Shunichi Fukuzumi | * |
dc.date.accessioned | 2016-08-28T10:08:39Z | - |
dc.date.available | 2016-08-28T10:08:39Z | - |
dc.date.issued | 2013 | * |
dc.identifier.issn | 0010-8545 | * |
dc.identifier.other | OAK-9893 | * |
dc.identifier.uri | https://dspace.ewha.ac.kr/handle/2015.oak/223552 | - |
dc.description.abstract | Electron-transfer properties of heme and non-heme high-valent metal-oxo complexes are overviewed in relation to their reactivity toward oxidation of substrates. The rate constants of electron transfer from a series of electron donors to various heme and non-heme high-valent metal-oxo complexes such as compound I and compound II of horseradish peroxidase (HRP), (TMP)MnIV(O) ((TMP=tetramesityl-porphyrinate dianion), (TBP8Cz)MnV(O) (TBP8Cz=octa-tert-butylphenylcorrolazinate trianion) and [(L)FeIV(O)]2+, where L=TMC, 1,4,8,11-tetra-methyl-1,4,8,11-tetraazacyclotetradecane; Bn-TPEN, N-benzyl-N,N',N'-tris(2-pyridylmethyl)ethane-1,2-diamine; N4Py, N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine; bisp, 3,7-diazabicyclo[3.3.1]nonane) were evaluated in light of the Marcus theory of electron transfer in order to determine the reorganization energy (λ) for electron transfer. The λ value increases in the order: 1.3eV (compound I of HRP), 1.53eV [(TBP8Cz)MnV(O)], 1.6eV (compound II of HRP), 1.7eV [(TMP)MnIV(O)], 2.05eV [(bisp)FeIV(O)]2+, 2.37eV [(TMC)FeIV(O)]2+), 2.55eV ([(Bn-TPEN)FeIV(O)]2+), 2.74eV ([(N4Py)FeIV(O)]2+). The λ value of compound I of HRP is the smallest among those of high-valent metal-oxo complexes, because the site of the reduction is on the porphyrin ligand, whereas the site of the reduction is on the metal for the other high-valent metal-oxo complexes. The λ values of high-valent metal-oxo porphyrins are generally smaller than those of non-heme iron(IV)-oxo complexes. The effects of Lewis acidic metal ions and Brønsted acids on the one-electron reduction of high-valent metal-oxo complexes are also overviewed in relation to their enhancement of the oxidizing ability towards reductants. © 2012 Elsevier B.V. | * |
dc.language | English | * |
dc.title | Electron-transfer properties of high-valent metal-oxo complexes | * |
dc.type | Review | * |
dc.relation.issue | 41527 | * |
dc.relation.volume | 257 | * |
dc.relation.index | SCI | * |
dc.relation.index | SCIE | * |
dc.relation.index | SCOPUS | * |
dc.relation.startpage | 1564 | * |
dc.relation.lastpage | 1575 | * |
dc.relation.journaltitle | Coordination Chemistry Reviews | * |
dc.identifier.doi | 10.1016/j.ccr.2012.07.021 | * |
dc.identifier.wosid | WOS:000316518900010 | * |
dc.identifier.scopusid | 2-s2.0-84875051709 | * |
dc.author.google | Fukuzumi S. | * |
dc.contributor.scopusid | Shunichi Fukuzumi(35430038100;58409757400) | * |
dc.date.modifydate | 20240401081001 | * |